Process for dyeing fibrous materials with aqueous cation active latices containing pigment



United States Patent 2,898,239 PROCESS FOR DYEING FIBROUS MATERIALS WITH AQUEOUS CATION ACTIVE LATICES CONTAINING PIG MENT Georg Sulzer and Peter Guertler, Basel, Willy Fatzer, Bottmiugen, and Arthur Maeder, Basel, Switzerland No Drawing. Application November 13, 1956 Serial No. 621,514

Claims priority, application Switzerland November 30, 1955 8 Claims. (Cl. 117-161) This invention relates to a process for dyeing with pigments and preparations suitable therefor.

This invention provides a process in which valuable pigment dyeings are obtained when aqueous dyebaths are used which contain pigments dispersed with cation-active dispersing agents and as binding agent a cation-active latex of a polymerizable plastic or an aqueous dispersion, produced with a cation-active dispersing agent, of a derivative, insoluble in water but soluble in organic solvents, of a formaldehyde condensation product of an amino compound yielding with formaldehyde hardenabl'e resins and, when a hardenable compound is present, hardening at elevated temperature after drying. The dyeings obtainable according to. the invention. are distinguished as a rule by good fastness to migration and satisfactory to good fastness to washing. In the present process it is very advantageous to use water-soluble formaldehyde condensation products of an amino. compound yielding with formaldehyde harden-able resins or water-soluble derivative thereof, whereby the fastness properties of the dyeings can be further increased.

For the preparation of cation-active polymer latices such polymers can be used as contain no. groups. which render the same cation-active but which are dispersed with, cation-active dispersing. agents. Preferably such are used; as contain cation-active groups. The polymers can be homo or co-polymers. from monomeric compounds with the atom grouping for example from vinyl esters of organic acids such asvinyl acetate, vinyl; formate, vinyl butyrate or vinyl benz oate or also from vinyl alkyl ketones, vinyl;halide s, such as vinyl chloride or vinyl fluoride, vinylidene-chloride or vinyl ar-yl. compounds such as styrene and substituted styrenes, oralso from; compounds of the acrylic acid methacrylic acid series, such as esters from acrylic acid. and alcohols or phenols, for example ethyl acrylate, butyl acrylate or dodecyl acrylate. Further monomeric compounds that can, serve for the synthesis. oi the polymen are. c y o u l t. c y m n erivative substituted on the amide nitrogen, also analogous derivatives of methacrylic acid, 0L Qh101'2lC'IY1lQ acid, crotonic acid, male i m c d; fina ly p vmeriz e; fines such: as isobutylene, butadiene, Z-chloro-butadiene or heterocyclic compounds, such as the various vinyl pyridines. The manufacture of binary, ternary or more compligatedly constructed copolymers in emulsion: form is known so that it is not; necessaryto describe it further. The following area few suitable copolym ers:

(a) Copolymer from 66, parts of v n.-butyl, acrylate, 12 parts of styrene and 22 parts of vinyl isobutyl ether,

(b) Copolymer from 70 parts of asym. dichlorethene and. 30 parts of butyl acrylate.

(c) Copolymer from- 50 parts of asym. dichlorethene, 45 parts of butyl acrylateand 5 parts of; acrylamide,

(d) Copolymer from 52 parts. of vinyl chloride, 35

parts of. butyl acrylate, 7 parts of methyl acrylate and 6 parts ofv acrylamide.

They are preferably derived Patented Aug. 4, 1959 Quaternary ammonium compounds, such as cetyldimethylbenzylammonium chloride, cetyl-trimethyl-arnmonium bromide, p-(trimethylammonium)-benzoic acid cetyl ester methosulfate, cetylpyridinium methosulfate, octadecyltrimethylammonium bromide or the quaternary compound from diethyl sulfate and triethanolamine tristearate are also suitable.

The manufacture of latices of polymerswith cationactive groups is known per se; such products are described for example in US. patent applications Ser. No. 464,599, filed October 25, 1954, by A. Maeder; Ser. No. 464,608, filed October 25, 1954, by A. Maeder; Ser. No. 464,600, filed October 25, 1954, by A. Maeder et a1 and Ser. No. 556,017, filed December 28, 1955, by A. Maeder et al.

The above mentioned derivatives of formaldehyde condensation products of an amino compound yielding hardenable resins with formaldehyde, which derivatives are insoluble in Water but soluble in organic solvents, are likewise used in. the form of dispersions. These derivatives can be derived on one hand from formaldehyde condensation products of urea, thiourea, guanidine, acetylene-di-urea, dicyandiamide or uron, or also from amino-triazines such as melamine or from guanamines' such as acetoguanamine, benzoquanamine or forrnoguanamine, and on the other hand from alcohols immiscible with water, such as butyl alcohol, amyl alcohol, hexyl alcohol, cyclohexanol, benzyl alcohol, lauryl alcos hol, oleyl alcohol or abiethyl alcohol. In addition to the ether residues, the condensation products can also contain residues of high-molecular'acids, for example, stearic acid. When such high. molecular acid residues. are pres' ent, the compounds can also be derived, from. methylol ethers with, low-molecular water soluble alcohols. The manufacture of such condensation products is known. The manufacture of the aqueous dispersions can like- Wise take place with the use of the cation-active dispersing agents mentioned above.

The water-soluble formaldehyde condensation products.

pigments, such as vat dyestuif or azo dyestuff pigments,

in so far as they can be dispersed with a cation-active dispersing agent. As cation-active dispersing agents for the pigments, the above mentioned products are concerned.

In the application of hardenable compounds, there are advantageously added to the dye-baths hardening catalysts, for example ammonium salts of strong acids.

The hardening which is optionally carried out takes place,

under the customary conditions, for example at l60 C. for 2-10 minutes. The use of polymer latices is not always equivalent to. that. of hardenable resins. binding agent will be selected according as to. whether special effects are also desired, for examplev asregards softness or crease-resistance.

Dyeing according to the present invention can. take,

The

place under the customary dyeing conditions, for example by the exhaust process but preferably by the foulard process.

The fiber materials to be treated according to the invention are primarily fabrics of natural or regenerated cellulose, such as cotton, linen, artificial sill; or staple fiber, or also cellulose esters, such as acetate silk, Wool or synthetic fiber materials such as nylon, polyester fibers or polyacrylonitrile fibers.

The following examples illustrate the invention, the parts being by weight unless otherwise stated and the relation between parts by weight and parts by volume being the same as that between the kilogram and the liter:

Example 1 Cotton poplin is dyed on the foulard in a dye-bath containing per liter:

10 grams of a 15% dyestulf paste of copper phthalocyanine which is dispersed with [/3-(octadecenoylamido)- ethyl] -diethylmethylammonium-methosulfate,

grams of a 70% emulsion of a methylolmelamine-allylether modified with soya fatty acid, emulsification having been carried out with of [fi-(octadecenoylamido) -ethyl] -diethylmethylammonium-methosulfate and 4 grams of ammonium nitrate.

Dyeing is carried out on the foulard up to 80% uptake of liquid, drying is effected on a frame and hardening carried out for 5 minutes at 150 C.

A level blue dyeing is obtained of good migration fastness and satisfactory fastness to washing.

Example 2 (a) The process is conducted as described in Example 1 but there are used: 40 grams per liter of a copolymer latex with 40% dry content, from 10 parts of the quaternary compound from acrylic acid (3-diethylaminopropyl)-arnide and chloracetamide, 150 parts of isobutyl acrylate and 40 parts of acrylonitrile with ['y-lauroylamido) propyl] diethylmethyl ammonium methosulfate as emulsifier.

(b) The process is conducted as described in Example 1 but there are used: 10 grams per liter of a copolymer latex with 40% dry content, from 90 parts of vinyl acetate and 10 parts of the quaternary compound from acrylic acid-(3-diethylaminopropyl)-amide and chloracetamide with ['y (lauroylamido) propylJ-trimethylammonium-methosulfate as emulsifier.

(c) The process is conducted as described in Example 1 but there are used: 40 grams per liter of a copolymer latex with 40% dry content, from 50 parts of vinyl acetate, 40 parts of n-butyl acrylate and 10 parts of the quaternary compound from acrylic acid-(3-diethylaminopropyl)-amide and chloracetamide with ['y-(stearoylamido) propyl] dimethyl (fi-hydroxyethyl) ammonium phosphate as emulsifier.

(a') The process is conducted as described in Example 1 but there are used: 40 grams per liter of the latex mentioned under (a) and 40 grams per liter of a Watersoluble methyl ether of a urea-formaldehyde condensation product constaining more than 2 mols formaldehyde condensed per mol of urea.

(e) The process is conducted as described in Example 1 but there are used: 10 grams per liter of the latex mentioned under (b) and 40 grams per liter of a watersoluble methyl ether of a urea-formaldehyde condensation product containing more than 2 mols formaldehyde consensed per mol of urea.

(f) The process is conducted as described in Example 1 but there are used: 10 grams per liter of the latex mentioned under (6) and 40 grams per liter of a watersolube methyl ether of a urea-formaldehyde condensation product containing more than 2 mols formaldehyde condensed per mol of urea.

What is claimed is:

l. A process for dyeing fibrous material with pigments, which comprises contacting the material with an aqueous composition of matter which contains a pigment dispersed with a cation-active dispersing agent and, as a pigment binder, only one member selected from the group consisting of (a) a cation-active latex of a flexible elastic polymerization plastic which has been obtained by polymerization of ethylenically unsaturated compounds and which plastic is the sole water-insoluble constituent in said latex, and of (b) an aqueous dispersion, produced with a cation-active dispersing agent, of a water-insoluble derivative which is soluble in organic solvents of a condensation product of formaldehyde with an aminotriazine; drying the material and heating to harden the composition applied, when a hardenable compound is used; the amount of binder used being about 3.5 to about 16 parts by weight per 1000 parts of the aqueous composition, said parts by weight being calculated on the dry content of the binder.

2. A process for dyeing fibrous material with pigments, which comprises contacting the material with an aqueous composition of matter which contains a pigment dispersed with a cation-active dispersing agent and, as pigment binders (I), only one member selected from the group consisting of (a) a cation-active latex of a flexible elastic polymerization plastic which has been obtained by polymerization of ethylenically unsaturated compounds and which plastic is the sole water-insoluble constituent in said latex, and of (b) an aqueous dispersion, produced with a cation-active dispersing agent, of a waterinsoluble derivative which is soluble in organic solvents of a condensation product of formaldehyde with an aminotriazine and (II) a member selected from the group consisting of water-soluble condensation products of formaldehyde with an aminotriazine, water-soluble condensation products of formaldehyde with a urea and water-soluble ethers of such urea and aminotriazine condensation products; drying the material and heating to harden the composition applied; the amount of binders used being about 4 to about 16 parts by weight of binder (I) and about 40 parts by weight of binder (II) per 1000 parts of the aqueous composition, said parts by weight being calculated on the dry content of the binder.

3. A process for dyeing fibrous materials with pigments, which comprises contacting the material with an aqueous composition of matter which contains a pigment dispersed with a cation-active dispersing agent and, as a pigment binder a cation-active latex of a flexible elastic polymerization plastic which itself contains no cationactive groups but is dispersed with a cation-active dispersing agent and has been obtained by polymerization of ethylenically unsaturated compounds and which plastic is the sole water-insoluble constituent in said latex, and drying the material; the amount of binder used being about 4 to about 16 parts by weight per 1000 parts of the aqueous composition, said parts by weight being calculated on the dry content of the binder.

4. A process for dyeing fibrous materials with pigments, which comprises contacting the material with an aqueous composition of matter which contains a pigment dispersed with a cation-active dispersing agent and as a pigment binder a cation-active latex of a flexible elastic polymerization plastic wherein the polymer itself contains cation-active groups and has been obtained by polymerization of ethylenically unsaturated compounds and which plastic is the sole Water-insoluble constituent in said latex, and drying the material; the amount of binder used being about 3.5 to 16 parts by weight per 1000 parts of the aqueous composition, said parts by weight being calculated on the dry content of the binder.

5. A process for dyeing fibrous materials with pigments, which comprises contacting the material with an aqueous composition of matter which contains a pigment dispersed with a cation-active dispersing agent and as a pigment binder a latex of a copolymerization product from parts of the quaternary compound from acrylic acid-(3-diethylamino-propyl)-amide and chloracetamide, 150 parts of isobutyl acrylate and 40 parts of acrylonitrile with ['y-(lauroylamido-)propyl]-diethy1-methylammonium-methosulfate as emulsifier; and drying the materiaL'the amount of the binder used being about 16 parts by Weight per 1000 parts of the aqueous composition, said parts by weight being calculated on the dry content of the binder.

6. A process for dyeing fibrous materials with pigments, which comprises contacting the material with an aqueous composition of matter which contains a pigment dispersed with a cation-active dispersing agent and as pigment binders (I) a latex of a copolymerization prodnot from 90 parts of vinyl acetate and 10 parts of the quaternary compound from acrylic acid-(3-diethylaminopropyl)-amide and chloracetamide with [v-(lauroyl-amido)-propy1 trimethylammonium methosulfate as emulsifier and (II) a water soluble methyl ether of a urea-formaldehyde condensation product containing more than 2 mols formaldehyde condensed per mol of urea; drying the material and heating to harden the composition applied, the amount of the binders used being about 4 parts by weight of binder (I) and about 40 parts by weight of binder-(II) per 1000 parts of the aqueous composition, said parts by weight being calculated on the dry content of the binders.

7. A process for dyeing fibrous materials with pigments, which comprises contacting the material with an aqueous composition of matter which contains a pig-- ment dispersed with a cation-active dispersing agent and as a pigment binder an aqueous dispersion, produced with a cation-active dispersing agent, of a water-insoluble ether of a methylol melamine which is soluble in organic solvents; drying the material and heating to harden the composition applied, the amount of the binder used being about 3.5 parts by Weight per 1000 parts of the aqueous composition, said parts by Weight being calculated on the dry content of the binder.

8. A process for dyeing fibrous materials with pigments, which comprises contacting the material with an aqueous composition of matter which contains a pigment dispersed with a cation-active dispersing agent and as a. pigment binder an aqueous dispersion, produced with [B (octadecenoyl amido) ethyl] diethyl methylammonium-methosulfate, of a methylol-melamine-allylether modified with soya fatty acid; drying the material and heating to harden the composition applied, the amount of the binder used being about 3.5 parts by weight per 1000 parts of the aqueous composition, said parts by weight being calculated on the dry content of the binder.

References Cited in the file of this patent UNITED STATES PATENTS 2,614,086 Jones Oct. 14, 1952 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,898,239 August 4, 1959 Georg Sulzer et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

In the grant, lines 1 to 3, for Georg Sulzer and Peter Guertler, of Basel, Willy Fatzer, of Bottmingen, and Arthur Maeder, of Basel, Switzerland, read -Georg Sulzer and Peter Guertler, of Basel Willy Fatzer, of Bottmingen, and Arthur Maeder, of Basel, Switzerland, assignors to diba Limited, of Basel, Switzerland, a Swiss firm,; lines 12 and 13, for Georg Sulzer, Peter Guertler, Willy Fatzer, and Arthur Maeder, their heirs read Ciba Limited, their heirs,-; in the heading to the printed specification, lines 5 and 6, for Georg Sulzer and Peter Guertler, Basel, Willy Fatzer, Bottmingen, and Arthur Maeder, Basel, Switzerland read Georg Sulzer and Peter Guertler, Basel, Willy Fatzer, Bottmingen, and Arthur Maeder, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm; in the printed specification, column 3, line 62, for constainmg read containing; line 69, for consensed read condensed-.

Signed and sealed this 24th day of May 1960.

[smart] Attest: V KARL H. AXLINE, ROBERT C. WATSON, Attestz'ng Oyficer. Gammissz'ouer of Patents. 

1. A PROCESS FOR DYEING FIBROUS MATERIAL WITH PIGMENTS, WHICH COMPRISES CONTACTING THE MATERIAL WITH AN AQUEOUS COMPOSITION OF MATTER WHICH CONTAINS A PIGMENT DISPERED WITH A CATION-ACTIVE DISPERSING AGENT AND, AS A PIGMENT BINDER, ONLY ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF (A) A CATION-ACTIVE LATEX OF A FLEXIBLE ELASTIC POLYMERIZATION PLASTIC WHICH HAS BEEN OBTAINED BY POLYMERIZATION OF ETHYLENICALLY UNSATURATED COMPOUNDS AND WHICH PLASTIC IS THE SOLE WATER-INSOLUBLE CONSTITUENT IN SAID LATEX, AND OF (B) AN AQUEOUS DISPERSION, PRODUCED WITH A CATION-ACTIVE DISPERSING AGENT, OF A WATER-INSOLUBLE DERIVATIVE WHICH IS SOLUBLE IN ORGANIC SOLVENTS OF A CONDENSATION PRODUCT OF FORMALDEHYDE WITH AN AMINOTRIAZINE; DRYING THE MATERIAL AND HEATING TO HARDEN THE COMPOSITION APPLIED, WHEN A HARDENABLE COMPOUND IS USED; THE AMOUNT OF BINDER USED BEING ABOUT 3.5 TO ABOUT 16 PARTS BY WEIGHT PER 1000 PARTS OF THE AQUEOUS COMPOSITION, SAID PARTS BY WEIGHT BEING CALCULATED ON THE DRY CONTENT OF THE BINDER. 